1. Field of the Invention
This invention relates to new crystalline molecular sieve zeolite compositions, having a pore size of from about 8 to at least 10 Angstrom units, containing at least titanium as an octahedral site in the framework structure; methods for preparing the same; uses thereof such as organic compound conversions therewith, especially hydrocarbon conversions, ion exchange applications, removal of metal ions from solutions thereof, removal of gases in both a selective and non-selective mode, including storage of the same; and removal of hydrocarbons from a non-hydrocarbon media, e.g., water. The novel materials of this invention possess a framework which contains octahedrally coordinated titanium alone or with at least one other metal in an octahedrally coordinated state and at least silicon in the framework in a tetrahedrally coordinated state.
2. Background of the Invention and Prior Art
Since the discovery by Milton and coworkers (U.S. Pat. No. 2,882,243 and U.S. Pat. No. 2,882,244) in the late 1950's that aluminosilicate systems could be induced to form uniformly porous, internally charged crystals, analogous to molecular sieve zeolites found in nature, the properties of synthetic aluminosilicate zeolite molecular sieves have formed the basis of numerous commercially important catalytic, adsorptive and ion-exchange applications. This high degree of utility is the result of a unique combination of high surface area and uniform porosity dictated by the "framework" structure of the zeolite crystals coupled with the electrostatically charged sites induced, by tetrahedrally coordinated Al.sup.+3. Thus, a large number of "active" charged sites are readily accessible to molecules of the proper size and geometry for adsorptive or catalytic interactions. Further, since charge compensating cations are electrostatically and not covalently bound to the aluminosilicate framework, they are generally exchangeable for other cations with different inherent properties. This offers wide latitude for modification of active sites whereby specific adsorbents and catalysts can be tailormade for a given utility.
In the publication "Zeolite Molecular Sieves", Chapter 2, 1974, D. W. Breck hypothesized that perhaps 1,000 aluminosilicate zeolite framework structures are theoretically possible, but to date only approximately 150 have been identified. While compositional nuances have been described in publications such as U.S. Pat. Nos. 4,524,055, 4,603,040 and U.S. Pat. No. 4,606,899, totally new aluminosilicate framework structures are being discovered at a negligible rate. Of particular importance to fundamental progress in the catalysis of relatively large hydrocarbon molecules, especially fluid cracking operations, is the fact that it has been a generation since the discovery of any new large pored aluminosilicate zeolite.
With slow progress in the discovery of new wide pored aluminosilicate based molecular sieves, researchers have taken various approaches to replace aluminum or silicon in zeolite synthesis in the hope of generating either new zeolite-like framework structures or inducing the formation of qualitatively different active sites than are available in analogous aluminosilicate based materials. While progress of academic interest has been made from different approaches, little success has been achieved in discovering new wide pore molecular sieve zeolites.
It has been believed for a generation that phosphorus could be incorporated, to varying degrees, in zeolite type aluminosilicate frameworks. In the more recent past (JACS 104 pp. 1146 (1982); Proceedings of the 7th International Zeolite Conference, pp. 103-112, 1986) E. M. Flanigan and coworkers have demonstrated the preparation of pure aluminophosphate based molecular sieves of a wide variety of structures. However, the site inducing Al.sup.+3 is essentially neutralized by the P.sup.+5, imparting a +1 charge to the framework. Thus, while a new class of "molecular sieves" was created, they are not zeolites in the fundamental sense since they lack "active" charged sites.
Realizing this inherent utility limiting deficiency, for the past few years the molecular sieve research community has emphasized the synthesis of mixed aluminosilicate-metal oxide and mixed aluminophosphate-metal oxide framework systems. While this approach to overcoming the slow progress in aluminosilicate zeolite synthesis has generated approximately 200 new compositions, all of which suffer either from the site removing effect of incorporated P.sup.+5 or the site diluting effect of incorporating effectively neutral tetrahedral +4 metals into an aluminosilicate type framework. As a result, extensive research by the molecular sieve research community has failed to demonstrate significant utility for any of these materials.
A series of zeolite-like "framework" silicates have been postulated, some of which have larger uniform pores than are observed for aluminosilicate zeolites. (W. M. Meier, Proceedings of the 7th International Zeolite Conference, pp. 13-22 (1986).) While this particular synthesis approach produces materials which, by definition, totally lack active, charged sites, back implementation after synthesis would not appear out of the question although little work appears in the open literature on this topic.
Another and most straightforward means of potentially generating new structures or qualitatively different sites than those induced by aluminum would be the direct substitution of some other charge inducing species for aluminum in zeolite-like structures. To date the most notably successful example of this approach appears to be boron in the case of ZSM-5 analogs, although iron has also been claimed in similar materials. (EPA 68,796 (1983), Taramasso et al; Proceedings of the 5th International Zeolite Conference; pp. 40-48 (1980)); J. W. Ball et al; Proceedings of the 7th International Zeolite Conference; pp. 137-144 (1986); U.S. Pat. No. 4,280,305 to Kouenhowen et al. Unfortunately, the low levels of incorporation of the species substituting for aluminum usually leaves doubt if the species are occluded or framework incorporated.
In 1967, Young in U.S. Pat. No. 3,329,481 reported that the synthesis of charge bearing (exchangeable) titanium silicates under conditions similar to aluminosilicate zeolite formation was possible if the titanium was present as a "critical reagent"+III peroxo species. While these materials were called "titanium zeolites" no evidence was presented beyond some questionable X-ray diffraction (XRD) patterns and his claim has generally been dismissed by the zeolite research community. (D. W. Breck, Zeolite Molecular Sieves, p. 322 (1974); R. M. Barrer, Hydrothermal Chemistry of Zeolites, p. 293 (1982); G. Perego et al, Proceedings of 7th International Zeolite Conference, p. 129 (1986).) For all but one end member of this series of materials (denoted TS materials), the presented XRD patterns indicate phases too dense to be molecular sieves. In the case of the one questionable end member (denoted TS-26), the XRD pattern might possibly be interpreted as a small pored zeolite, although without additional supporting evidence, this appears extremely questionable.
A naturally occurring alkaline titanosilicate identified as "Zorite" was discovered in trace quantities on the Kola Peninsula in 1972 (A. N. Mer'kov et al; Zapiski Vses Mineralog. Obshch., pages 54-62 (1973)). The published XRD pattern was challenged and a proposed structure reported in a later article entitled "The OD Structure of Zorite", Sandomirskii et al, Sov. Phys. Crystallogr. 24 (6), Nov-Dec 1979, pages 686-693.
No further reports on "titanium zeolites" appeared in the open literature until 1983 when trace levels of tetrahedral Ti(IV) were reported in a ZSM-5 analog. (M. Taramasso et al; U.S. Pat. No. 4,410,501 (1983); G. perego et al; Proceedings of the 7th International Zeolite Conference; p. 129 (1986).) A similar claim appeared from researchers in mid-1985 (EPA 132,550 (1985).) More recently, the research community reported mixed aluminosilicate-titanium(IV) (EPA 179,876 (1985); EPA 181,884 (1985) structures which, along with TAPO (EPA 121,232 (1985) systems, appear to have no possibility of active titanium sites because of the titanium coordination. As such, their utility is highly questionable.
That charge bearing, exchangeable titanium silicates are possible is inferred not only from the existence of exchangeable alkali titanates and the early work disclosed in U.S. Pat. No. 3,329,481 on ill defined titanium silicates but also from the observation (S. M. Kuznicki et al; J. Phys. Chem.; 84; pp. 535-537 (1980)) of TiO.sub.4 - units in some modified zeolites.
David M. Chapman, in a speech before 11th North American Meeting of the Catalysis Society in Dearborn, Mich. (1989) gave a presentation wherein a titanium aluminosilicate gel was crystallized with Chapman claiming all the aluminum was segregated into analcime (an ultra-small pored aluminosilicate) and not incorporated into any titanium-bearing phase such as his observed analog of the mineral vinogradovite which was a pure titanium silicate. It is noted that vinogradovite, as found in nature, has been reported to contain aluminum. However, neither the synthetic analog of vinogradovite nor the mineral vinogradovite is a molecular sieve.
Chapman et al, Zeolites, 1990, Vol. 10, November/December, discloses small-pored titanium silicate materials including zorite.
Chapman, U.S. Pat. No. 5,015,453, discloses titanium silicate materials which are structurally different than the instant large pored materials.
A major breakthrough in the field of large pored titanium silicate molecular sieves is disclosed and claimed in U.S. Pat. No. 4,853,202. The crystalline titanium silicate large pored molecular sieve of said patent, hereafter designated ETS-10, contains no deliberately added alumina but may contain very minor amounts of alumina due to the presence of impurities.
A second breakthrough is disclosed and claimed in copending application Ser. No. 07/373,855, filed on Jun. 29, 1989, the entire disclosure of which is herein incorporated by reference. Said application relates to large-pored sieves with charged octahedral titanium and charged tetrahedral aluminum sites identified as ETAS-10.